<p>III-V nanowire (NW) ensemble devices were fabricated using novel approaches to address key NW optoelectronic issues concerning electrical contacts, doping, surface effects and underlying electrostatics physics.</p> <p>NWs were first embedded in a filling medium, thus achieving low sheet resistance front contacts while preventing shunts. Various filling materials were assessed for porosity, surface roughness and thermal stability, giving Cyclotene as an ideal filing material. Sonication was also introduced as a novel method to achieve perfect planarization.</p> <p>The presence of the Cyclotene also enabled the NWs to be characterized precisely and easily by secondary ion mass spectrometry (SIMS) to give the NW dopant concentration with excellent spatial resolution. Additionally, SIMS characterization demonstrated the ability to characterize the height uniformity of individual segments in a heterostructure NW ensemble.</p> <p>The focus of the work shifted towards surface effects on NW device performance. Therefore, Poisson's equation was solved to provide a comprehensive model of NW surface depletion as a function of interface state density, NW radius and doping density. Underlying physics was examined where surface depletion was found to significantly reduce the conductivity of thin NWs, leading to carrier inversion for some.</p> <p>This model was then applied in conjunction with a transport model to fit current-voltage curves of an AlInP-passivated GaAs NW ensemble device. A 55% decrease in surface state density was achieved upon passivation, corresponding to an impressive four order of magnitude increase in the effective carrier concentration. Additionally, conventional and time-resolved photoluminescence measurements showed intensity and carrier lifetime improvement greater than 20x upon passivation.</p> <p>Finally, the model was extended to describe radial pn junction NWs with surface depletion to give radial energy band profiles for any arbitrary set of NW parameters. Specific cases were analyzed to extract pertinent underlying physics, while the built-in potential was optimized for the design for an optimal device.</p> / Doctor of Philosophy (PhD)

<p>Surface preparation and its exposure to different processing conditions is a key step in heterogeneous integration of electronics, photonics, fluidics and/or mechanical components for More-than-Moore applications. Therefore, it is critical to understand how various processing and environmental conditions affect the surface properties of bonding substrates. In this thesis, the effects of oxygen reactive-ion etching (O₂ RIE) plasma followed by storage in ambient and 98% relative humidity on some key surface properties such as roughness, water contact angle, hardness, and the elemental and compositional states of three materials – silicon (Si), silicon dioxide (SiO₂) and glass – are investigated to analyze their influence on bondability. Lower O₂ RIE plasma activation times cause low surface roughness, high surface reactivity and high hydrophilicity of Si, SiO₂ and glass. The decrease of hardness of Si and SiO₂ with increased activation time is attributed to higher surface roughness and formation of amorphous layers of Si. While contact angle and surface roughness results show correlation with bondability, the role of hardness on bondability requires further investigation. The high-resolution X-ray Photoelectron Spectroscopy (XPS) spectra of O₂ RIE treated Si, SiO₂ and glass showed the presence of Si(-O)₂ resulting in highly reactive surfaces. The high surface reactivity of Si, SiO₂ and glass obtained from oxygen plasma activation at lower activation times can result in better bondability. Also, the ambient humidity-induced Si(-OH)_x plays an important role in the hydrophilic wafer bonding of Si and SiO₂ which may require a low temperature heating.</p> / Master of Applied Science (MASc)

Numerical simulations of current-voltage characteristics of nanowire CdS/CdTe solar cells are performed as a function of temperature using SCAPS-1D. This research compares the experimental current-voltage (I-V) characteristics with the numerical (I-V) simulations obtained from SCAPS-1D at various temperatures. Various device parameters were studied which can affect the efficiency of the nanowire-CdS/CdTe solar cell. It was observed that the present simulated model explains the important effects of these solar cell devices, such as the crossover and the rollover effect. It was shown that the removal of defect in i-SnO2 is responsible for producing the crossover effect. In the past, the rollover effect has been explained by using back to back diode model in the literature. In this work, simulations were performed in order to validate this theory. At the back electrode, the majority carrier barrier height was varied from 0.4 to 0.5 eV, the curve corresponding to the 0.5 eV barrier showed a strong rollover effect, while this effect disappeared when the barrier was reduced to 0.4 eV. Thus, it was shown that the change of barrier height at the contact is a critical parameter in the rollover effect.

Scanning-electron-beam lithography (SEBL) is the primary technology to generate arbitrary features at the nano-scale. However, pattern placement accuracy still remains poor compared to its resolution due to the open-loop nature of SEBL systems. Vibration, stray electromagnetic fields, deflection distortion and hysteresis, substrate charging, and other factors prevent the electron-beam from reaching its target position and one has no way to determine the actual beam position during patterning with conventional systems. To improve the pattern placement accuracy, spatial-phase-locked electron-beam lithography (SPLEBL) provides feedback control of electron-beam position by monitoring the secondary electron signal from electron-transparent fiducial grids on the substrate. While scanning the electron beam over the fiducial grids, the phase of the grid signal is analyzed to estimate the electron-beam position error; then the estimates are sent back to beam deflection system to correct the position error. In this way, closed-loop control is provided to ensure pattern placement accuracy. The implementation of spatial-phase-locking on high speed field-programmable gate array (FPGA) provides a low-cost method to create a nano-manufacturing platform with 1 nm precision and significantly improved throughput. Shot-to-shot, or pixel-to-pixel, dose variation during EBL is a significant practical and fundamental problem. Dose variations associated with charging, electron source instability, optical system drift, and ultimately shot noise in the beam itself conspire to increase critical dimension variability and line width roughness and to limit the throughput. It would be an important improvement to e-beam patterning technology if real-time feedback control of electron-dose were provided to improve pattern quality and throughput even beyond the shot noise limit. A novel approach is proposed in this document to achieve the real-time dose control based on the measurement of electron arrival at the sample to be patterned, rather than from the source or another point in the electron-optical system. A dose control algorithm, implementation on FPGA, and initial experiment results for the real-time feedback dose control on the e-beam patterning tool is also presented.

Surface-plasmon-resonance (SPR) sensors are widely used in biological, chemical, medical, and environmental sensing. This dissertation describes the design and development of dual-mode, self-referencing SPR sensors supporting two surface-plasmon modes (long- and short-range) which can differentiate surface binding interactions from bulk index changes at a single sensing location. Dual-mode SPR sensors have been optimized for surface limit of detection (LOD). In a wavelength interrogated optical setup, both surface plasmons are simultaneously excited at the same location and incident angle but at different wavelengths. To improve the sensor performance, a new approach to dual-mode SPR sensing is presented that offers improved differentiation between surface and bulk effects. By using an angular interrogation, both surface plasmons are simultaneously excited at the same location and wavelength but at different angles. Angular interrogation offers at least a factor of 3.6 improvement in surface and bulk cross-sensitivity compared to wavelength-interrogated dual-mode SPR sensors. Multi-mode SPR sensors supporting at least three surface-plasmon modes can differentiate a target surface effect from interfering surface effects and bulk index changes. This dissertation describes a tri-mode SPR sensor which supports three surface plasmon resonance modes at one single sensing position, where each mode is excited at a different wavelength. The tri-mode SPR sensor can successfully differentiate specific binding from the non-specific binding and bulk index changes.

Heterojunctions of CuInSe2 (CIS) nanowires with cadmium sulfide (CdS) were fabricated demonstrating for the first time, vertically aligned nanowires of CIS in the conventional Mo/CIS/CdS stack. These devices were studied for their material and electrical characteristics to provide a better understanding of the transport phenomena governing the operation of heterojunctions involving CIS nanowires. Removal of several key bottlenecks was crucial in achieving this. For example, it was found that to fabricate alumina membranes on molybdenum substrates, a thin interlayer of tungsten had to be inserted. A qualitative model was proposed to explain the difficulty in fabricating anodized aluminum oxide (AAO) membranes directly on Mo. Experimental results were used to corroborate this model. Subsequently, a general procedure to use any material that can be deposited using sputtering or evaporation as a back contact for nanowires grown using AAO templates was developed. Experimental work to demonstrate this by transferring thin AAO templates onto flexible Polyimide (PI) substrates was performed. This pattern transfer approach opens doors for a wide variety of applications on almost any substrate. Any material that can be deposited by physical means can then be used as a back contact. Electron-beam induced deposition using a liquid precursor (LP-EBID) was used to selectively grow preconceived patterns of compound semiconductor (CdS) nanoparticles. Stoichiometric CdS nanoparticle patterns were grown successfully using this method. They were structurally and optically characterized indicating high purity deposits. This approach is promising because it marries the precision of e-beam lithography with the versatility of solution based deposition methods.

New power applications for managing increasingly higher power levels require that more heat be removed from the power transistor channel. Conventional treatments for heat dissipation do not take into account the conversion of excess electron energy into longitudinal optical (LO) phonons, whose associated heat is stored in the channel unless such LO phonons decay into longitudinal acoustic (LA) phonons via a Ridley path. A two dimensional electron gas (2DEG) density of ~5×1012cm-2 in the channel results in a strong plasmon–LO phonon coupling (resonance) and a minimum LO phonon lifetime is experimentally observed, implying fast heat removal from the channel. Therefore, it is desirable to shift the resonance condition to higher 2DEG densities, and thereby higher power levels. The more convenient way to attain the latter is by widening the 2DEG density profile via heterostructure engineering, i.e. by using multiple channel heterostructures. A single channel heterostructure (GaN/AlN/AlGaN), a basic heterostructure used to obtain a 2DEG, exhibits a resonance condition at low 2DEG densities (~0.65×1012 cm-2). Successful widening of the 2DEG density xv profile was predicted by simulation results for two types of multiple (Al)GaN channel heterostructures, i.e. coupled channel GaN/AlN/GaN/AlN/AlGaN and dual channel GaN/AlGaN/AlN/AlGaN. Because of a reduction of carrier confinement, it is experimentally observed that control of the channel is moderate in the case of dual channel heterostructures. On the other hand, carrier confinement provides a better control of the channel in coupled channel heterostructures. Furthermore, unlike in a dual channel heterostructure, alloy scattering does not affect carrier transport properties, which results in a higher cut-off frequency. It was found experimentally that the coupled channel heterostructure successfully reaches resonance condition at a 2DEG density that is 23% higher than in a single channel heterostructure. Multiple channel heterostructures therefore provide a convenient way to shift the plasmon-LO phonon resonance to higher 2DEG densities. However, in our grown heterostructures, high power levels under optimal channel working conditions and minimum heat accumulation, all desirable benefits for the development of high power transistors, were only observed in coupled channel heterostructures.

Polímeros de coordenação têm atraído a atenção de pesquisadores na última década por conta de sua incrível versatilidade e virtualmente infinito número de possibilidades de combinação de ligantes orgânicos e centros metálicos. Estes compostos normalmente herdam as características magnéticas, eletrônicas e espectroscópicas de seus componentes base. Entretanto, apesar do crescente número de trabalhos na área, ainda são raros os polímeros de coordenação que apresentem condutividade elétrica. Para este fim, utilizou-se a N,N\'-bis(4-piridil)-1,4,5,8-naftaleno diimida, ou NDI-py, que pertence a uma classe de compostos rígidos, planares, quimicamente e termicamente estáveis e que já foram extensamente estudados por suas propriedades fotoeletroquímicas e semicondução do tipo n. O primeiro polímero de coordenação sintetizado, MOF-CoNDI-py-1, indicou ser um polímero linear, de estrutura 1D. O segundo, MOF-CoNDI-py-2, que conta com ácido tereftálico como ligante suporte, é um sólido cristalino com cela unitária monoclínica pertencente ao grupo espacial C2/c, determinado por difração de raios-X de monocristal. A rede apresenta um arranjo trinuclear de íons Co(II) alto spin com coordenados em uma geometria de octaedro distorcido, enquanto os ligantes NDI-py se encontram em um arranjo paralelo na estrutura, em distâncias apropriadas para transferência eletrônica. Com o auxílio de cálculo teóricos a nível de DFT, foi realizado um estudo aprofundado dos espectros eletrônicos e vibracionais, com atribuição das transições observadas, tanto para o MOF-CoNDI-py-2 quanto para o ligante NDI-py livre. A rede de coordenação absorve em toda a região do espectro eletrônico analisada, de 200 nm a 2500 nm, além de apresentar luminescência com característica do ligante. Dispositivos eletrônicos fabricados com um cristal do MOF-CoNDI-py-2 revelaram condutividades da ordem de 7,9 10-3 S cm -1, a maior já observada para um MOF. Além de elevada, a condutividade elétrica dos cristais demonstrou-se altamente anisotrópica, sendo significativamente menos condutor em algumas direções. Os perfis de corrente versus voltagem foram analisados em termos de mecanismos de condutividade, sendo melhores descritos por um mecanismo limitado pelo eletrodo to tipo Space-Charge Limited Current, concordando com a proposta de condutividade através dos planos de NDI-py na rede. A condutividade dos cristais também é fortemente dependente de luz, apresentando fotocondução quando irradiado por um laser vermelho, de 632 nm, enquanto apresenta um comportamento fotorresistivo frente a uma fonte de luz branca. Estes resultados, combinados, trazem um MOF em uma estrutura incomum e com elevada condutividade elétrica, modulada por luz, em medidas diretas de corrente. Não existem exemplos conhecidos de MOFs na literatura com estas características. / Coordination polymers have been a major topic in materials science during the past decade, thanks to their versatility and virtually infinite possible combinations between metal centers and organic ligands. These coordination polymers usually inherit the properties of their components, such as magnetic, spectroscopic and electronic characteristics. However, despite the increasing number of research papers in this topic, it is still hard to find coordination polymers featuring electronic conductivity. To achieve that, we used a naphthalene diimide derivative, N,N\'-bis(4-pyridyl)-1,4,5,8- naphthalene diimide or NDI-py, which belongs to a class of rigid, planar, thermally and chemically stable compounds, extensively studied due to their photoelectrochemical properties and their n-type semiconductivity. The first coordination polymer synthesised, MOF-CoNDI-py-1, was an amorphous linear polymer, with a 1D structure. Based on these observations, MOF-CoNDI-py-2 was synthesised by using terephthalic acid as a supporting ligand, and it is a crystalline solid which its monoclinic unit cell belongs to a C2/c space group, as determined by single crystal X-ray diffraction. This network features a trinuclear high-spin Co(II) unit, and each metal ion sits on a distorted octahedra coordination geometry, while the NDI-py ligands sit in a parallel arrangement, with distances suitable for electronic transfers. A detailed study of their vibrational and electronic spectra, supported by DFT calculations, was performed, as well as a full description and assignment of the observed bands. MOF-CoNDI-py-2 absorbs in the whole studied spectral region, from 200 nm to 2500 nm, while it also features a ligand-centered emission spectrum. Electronic devices built around its crystals revealed electric conductivities of 7.9 10 -3 S cm -1, which is, to the best of our knowledge, the highest for a MOF to this date. This conductivity is also highly anisotropic, being significantly less conductive in certain directions. The current versus voltage profiles were analysed in terms of known conduction mechanisms, with best fits when using an electrode-limited Space-Charge Limited Current mechanism, in agreement with the proposition that this conductivity happens through the NDI-py stacking planes. Additionally, this mechanism is influenced by an external light source, being a photoconductor with a red laser, 632 nm, and a photoresistor with a white light. Combined, these results bring a light-modulated, highly conductive MOF material with an unusual structure. As far as we know, there are no similar MOFs in the literature, which makes MOF-CoNDI-py-2 one of a kind.

This essay examines Swedish nursery children’s oral vocabulary knowledge in English. The aim is to investigate what they know and find the source to their knowledge. This essay will focus on the receptive and productive knowledge the children know based on the categories tested, how much children learn in their Zone of Proximal Development, how much they learn from context and how much does media and electronic devices influence their learning. The data of this essay were collected from interviews of 25 children and from questionnaires answered by their parents. The results of the study indicate that the children have more receptive knowledge of the English words tested. It also suggests that the productive knowledge they have is connected with the words that sound similar in Swedish and that children learn English from their surroundings such as siblings and parents, and from games on iPads and video clips from YouTube.

Este trabalho descreve o estudo de preparação dos filmes de polianilina, Pani, depositados pelo método de polimerização in-situ para serem utilizados em dispositivos poliméricos emissores de luz (PLEDs) e em sensores químicos e de flexão mecânica. É descrita a síntese química da Pani, a produção de filmes pelo método de polimerização in-situ, o estudo do seu crescimento usando a espectroscopia de UV-Vis e as características morfológicsa da superfície pela técnica de varredura de AFM. Filmes de Pani depositados pela técnica in-situ sobre eletrodos interdigitados foram caracterizados através de medidas de condutividade elétrica contínua e alternada em função da temperatura e da dopagem do material. Os resultados elétricos obtidos, típicos de sistemas sólidos desordenados, foram interpretados usando o modelo de condução de Dyre. Investigou-se o uso de filmes finos de Pani como camada injetora de portadores de carga em PLEDs para diferentes métodos de conversão do precursor poli(xilideno tetrahidrotiofeno), PTHT, em poli(-fenileno vinileno), PPV. Mostrou-se que a camada de Pani pode ser usada como janela transparente da emissão luminosa do PPV, o que diminui a tensão de operação do PLED e protege o eletrodo de ITO contra a corrosão durante o processo de conversão. São mostrados estudos exploratórios de sensores de Pani depositados sobre o substrato de poli (tereftalato de etileno) (PET) para aplicação em dispositivos para medidas de pH de solução e de flexão mecânica. / This work shows the study of Pani film prepared by the in-situ deposition technique aiming its use im polymeric light emission diodes (PLEDs) and in chemical sensors and of flection mechanics. The sysnthesis of the Pani, the production of films by the in-situ method, the film growth probed by UV-Vis spectroscopy and its surface morphology characteristics probed by the scanning AFM microscope are presented. Such in-situ films were deposited on the top of interdigitated electrodes and characterized usign ac and dc conductivity measurements as function of temperature and of the material doping level. The electric results were typical of non ordered materials and interpreted using the Dyre´s conduction model. It was investigated the use of Pani films as carrier layer injection in PLEDs employing different of conversion of poly(xylylidene tetrahydrothiophenium), PTHT, in to poly(-phenylene vinylene), PPV. It was showed that the Pani film act as a transparent window for the PPV light emission, the onset voltage of the PLED decreased and the Pani layers protects the ITO electrode against the corrosion during the conversion of the PTHT in to PPV. Exploratory studies were also performed using the Pani layer deposited on the top of a poly (ethylene terephtalate) substrate aiming its application for measuring the pH of a solution and as mechanical bending sensor.